CN108470632A - A kind of paper substrate electrode and preparation method thereof for ultracapacitor - Google Patents
A kind of paper substrate electrode and preparation method thereof for ultracapacitor Download PDFInfo
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- CN108470632A CN108470632A CN201810341113.6A CN201810341113A CN108470632A CN 108470632 A CN108470632 A CN 108470632A CN 201810341113 A CN201810341113 A CN 201810341113A CN 108470632 A CN108470632 A CN 108470632A
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- electrode
- papery
- substrate
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- ultracapacitor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The paper substrate electrode and preparation method thereof that the invention discloses a kind of for ultracapacitor, preparation method includes the following steps：A. select the paper wood of hydrophilic and oleophobic as papery substrate；B. the raw material including active electrode material, binder and solvent is uniformly mixed, electrode slurry is made；C., step b electrode slurrys are coated on to the obverse and reverse of step a papery substrates；D. semi-finished product obtained by step c are dried and are cut to get.The characteristic of papery substrate hydrophilic and oleophobic, enable the active electrode material that liquid electrolyte and papery substrate surface are covered compatible with；The binder mixed with active electrode material and solvent makes active electrode material have better adhesion effect, and bond strength higher, flexibility and stability are more preferable；The metal nano material of addition not only has the function of increasing surface area, but also can also play the role of support, is remarkably improved the capacitance of ultracapacitor；Simple production process, it is at low cost, it can be achieved that large-scale production.
Description
Technical field
The present invention relates to ultracapacitor fields, and in particular to a kind of for the paper substrate electrode of ultracapacitor and its preparation
Method.
Background technology
Ultracapacitor, also referred to as electrochemical capacitor, double layer capacitor etc. are between traditional capacitor and charging
A kind of novel energy storage apparatus between battery, energy storage is not required to via redox reaction, and is existed by electrolyte ion
Movement between electrode and electrolyte interface, at the electrode surface by charge adsorption, compared with traditional capacitor, it has larger
Capacity, than energy or energy density, wider operating temperature range and extremely long service life, and compared with accumulator, it
There is higher specific power again, and it is environmentally safe, also have charge/discharge rates fast, it is energy saving, safe, be not necessarily to manual maintenance etc.
Advantage.
There are many kinds of the constructions and preparation method of ultracapacitor, but its electrode is utilized in metallic substrates and covers mostly
Or attachment activity electrode material and it is manufactured, it is not only of high cost, and operating process and production technology it is more complex in addition some
Method is also difficult to realize large-scale production.However, the electrode basement of paper substrate ultracapacitor is then to use paper, it is a kind of i.e. use
Material is abandoned, relative to metallic substrates electrode, it not only has production cost low, but also can be used for being made very thin and small
Flexible super capacitor, and it is used for chip type integrated device.Such as the minimizing, is integrated of paper substrate flexible integration sensor, intelligence
The development of energyization will play its important function in electronic skin, biological medicine, wearable electronic product and aerospace.
Although the production cost of paper substrate ultracapacitor is low, at present simultaneously about the developmental achievement of paper substrate ultracapacitor
It is rare.The reason is that, using the ultracapacitors of paper substrates, there is following major defects：Paper substrates non-refractory,
And be difficult in paper surface covering and attachment activity electrode material, processing technology is complicated, and most liquid electrolytes are to papery base
The active electrode material that bottom surface is covered is difficult to be compatible with, it is often more important that paper substrate ultracapacitor all rests on laboratory mostly
Development phase, the technique for scribbling graphite linings in paper substrates in particular by pencil-lead was not only time-consuming but also bothersome, exists and is difficult to advise
The deficiency of modelling production etc..
Invention content
To overcome deficiencies of the prior art, the present invention provides a kind of paper substrate electrode for ultracapacitor
Preparation method is convenient for the attachment of active electrode material, and is conducive to large-scale production.The present invention is real by the following technical programs
It is existing：A kind of preparation method of paper substrate electrode for ultracapacitor, includes the following steps：
A. select the paper wood of hydrophilic and oleophobic as papery substrate；
B. the raw material including active electrode material, binder and solvent is uniformly mixed, electrode slurry is made；
C., electrode slurry described in step b is coated on to the obverse and reverse of the papery substrate described in step a；
D. semi-finished product obtained by step c are dried and are cut to get.
Preferably, raw material described in step b further includes metal nano material.
Preferably, the raw material is uniformly mixed by step b by homogenizer or dispersion machine, and is shaken by ultrasonic continuous
The electrode slurry obtained.
Preferably, include that following distribution is rapid successively in step c：
C1. the papery substrate described in step a is tensioned by transmitting device, and it is transmitted to rewinding dress from discharging device
It sets, wherein the transmission road from the discharging device to the material collecting device is additionally provided with the first spray equipment, the first roller successively from
Pressure device, the first drying unit, the second spray equipment and the second rolling device；
C2. by the first spray equipment described in step c1, electrode slurry described in step b is sprayed on the paper described in step a
The front of matter substrate, then it is by the first rolling device described in step c1 that the electrode slurry roll-in of spraying is smooth, finally lead to
The first drying unit described in step c1 is crossed to dry；
C3. by the second spray equipment described in step c1, electrode slurry described in step b is sprayed on the paper described in step a
The reverse side of matter substrate, then it is by the second rolling device described in step c1 that the electrode slurry roll-in of spraying is smooth.
Preferably, the transmission road described in step c1 is additionally provided with the second drying unit through place, and step d is dried by described second
Device dries semi-finished product obtained by step c.
Preferably, the drying temperature of step c2 and step d are 100~160 DEG C.
Preferably, the active electrode material described in step b includes in porous activated carbon, carbon nanotube, graphite and graphene
At least one.
A kind of paper substrate electrode for ultracapacitor, including papery substrate, the papery substrate are hydrophilic and oleophobic
The obverse and reverse of papery substrate, the papery substrate is attached with electrode coating, and the electrode coating is electric described in above-mentioned steps b
Pole slurry is formed.
The characteristic of papery substrate hydrophilic and oleophobic, the active electrode material for making liquid electrolyte be covered with papery substrate surface
It can be compatible with；The binder mixed with active electrode material and solvent can enhance active electrode material in paper
Bond strength, flexibility on matter substrate surface and stability, compared with bonding active electrode material separately through adhesive layer,
Make active electrode material that there is better adhesion effect, bond strength higher, flexibility and stability are more preferable；The metal of addition is received
Rice material not only has the function of increasing surface area, but also can also play the role of support, is remarkably improved ultracapacitor
Capacitance；By rotary shaft coating processes, in conjunction with the setting of drying unit, simple production process is at low cost, and production efficiency is high,
Good product consistency, qualification rate are high, it can be achieved that large-scale production.
Description of the drawings
Invention is further described in detail in the following with reference to the drawings and specific embodiments.
Fig. 1 is the cross-sectional view of paper substrate electrode of the embodiment of the present invention；
Fig. 2 is the cross-sectional view of the symmetrical ultracapacitor main part of paper substrate plane of the embodiment of the present invention；
Fig. 3 is the preparation method schematic diagram of paper substrate electrode of the embodiment of the present invention.
Each label corresponds to as follows, positive pole connecting plate 11, negative pole connecting plate 12, first electrode coating 21, second electrode in figure
Coating 22, papery substrate 3, discharging device 4, the first spray equipment 51, the second spray equipment 52, the first initiative roll shaft 61, first
Driven roll shaft 62, the first drying unit 71, the second drying unit 72, the second initiative roll shaft 81, the second driven roll shaft 82, transmission dress
9 are set, material collecting device 10.
Specific implementation mode
Below in conjunction with the accompanying drawings and the present invention is further described in embodiment：
As an example, the present embodiment is used for the paper substrate electrode of ultracapacitor, as shown in Figure 1, be plane symmetric form,
, by the paper wood of hydrophilic and oleophobic as papery substrate 3, the front of papery substrate 3 is attached with first electrode coating 21, reverse side attachment for it
It is by including active electrode material, binder to have second electrode coating 22, first electrode coating 21 and second electrode coating 22
Rear electrode slurry obtained is formed by evenly mixing with the raw material of solvent, and specifically, above-mentioned electrode slurry can be whole through spraying, roll-in
First electrode coating 21 and second electrode coating 22 are formed after flat and drying and processing.
Above-mentioned binder is when it is implemented, preferably from polyvinyl alcohol (PVA), polyethylene glycol (2000-4000), polypropylene
Any one of sour (PAA), carboxymethyl cellulose, Kynoar, polytetrafluoroethylene (PTFE), butadiene-styrene rubber etc..
Above-mentioned solvent is when it is implemented, preferably from N-Methyl pyrrolidone, N, N-METHYLFORMAMIDE, acetonitrile
(acetonitrile-ACN), vinyl carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl-methyl carbon
Acid esters (EMC), ethylene glycol, glycerine, methyl propanediol etc. it is any.
The porous fibre structure that papery substrate 3 has can enhance and other materials especially active electrode material, electricity
Solve the binding force of matter or even subsequent electronic device etc.；The binder mixed with active electrode material and solvent, can
Enhance bond strength, flexibility and stability of the active electrode material on paper substrates surface, is glued with separately through adhesive layer
Knot active electrode material is compared, and active electrode material is made to have a better adhesion effect, bond strength higher, flexibility and steady
It is qualitative more preferable；Electrode slurry obtained not only sprays conveniently, but also is flattened conducive to roll-in, keeps processing technology simpler, cost is more
It is low, and then it is conducive to large-scale production.
When it is implemented, active electrode material can be selected from one kind in porous activated carbon, carbon nanotube, graphite and graphene
Or it is several.A kind of preferred embodiment as active electrode material comprising graphite and graphene, the ratio of the two quality accounting
Example is graphite:Graphene=85%~95%:5%~15%, which is conducive to improve the capacitance of ultracapacitor.
Preferably, the raw material for preparing electrode slurry further includes metal nano material, when it is implemented, can will be micro (excellent
Choosing account for the 0.01%~1% of raw material gross mass) metal nano material and electrode material, binder, solvent be mixed together uniformly,
Electrode slurry is made.The metal nano material of addition not only has the function of increasing surface area, but also can also play the work of support
With (can improving the porosity of electrode such as in graphite, reduce graphite interlayer and be extruded and bond again
Possibility), be remarkably improved the capacitance of ultracapacitor.
Above-mentioned active metal nano material, electrode material, binder and solvent content when it is implemented, can distinguish successively
0.01%~1%, 5%~15%, 1%~8% and the 70%~90% of raw material gross mass is accounted for, the paper being worth by the proportioning raw material
Base electrode quality is very good, when being applied to ultracapacitor, can very significantly improve the capacitance of ultracapacitor.
As an example, by above-mentioned paper substrate application of electrode in the preparation symmetrical ultracapacitor of piece of paper base plane type
When, together refering to what is shown in Fig. 2, by being cut out by the above-mentioned paper substrate electrode of drying according to size needed for ultracapacitor is prepared
It cuts, such as cuts into the rectangle of 35 × 55mm sizes, be then dipped into electrolyte, and respectively in first electrode coating 21 and
The surface connection positive pole connecting plate 11 and negative pole connecting plate 12 (such as metal aluminum foil or copper sheet etc.) of two electrode coatings 22, in order to
Anode, negative terminal are drawn, finally crosses modeling post package into the symmetrical ultracapacitor of lamination piece of paper base plane type with plastic film.
The characteristic of 3 hydrophilic and oleophobic of papery substrate keeps the active electrode material that liquid electrolyte is covered with 3 surface of papery substrate fine
Ground is compatible with.
As an example, preparation method of the present embodiment for the paper substrate electrode of ultracapacitor, as shown in figure 3, according to
It is secondary to include the following steps：
A. select the paper wood of hydrophilic and oleophobic as papery substrate 3；
B. the raw material including active electrode material, binder and solvent is uniformly mixed, electrode slurry is made, preferably passes through
Above-mentioned raw materials are uniformly mixed by homogenizer or dispersion machine, 4~8h of incorporation time, and shake electrode obtained by ultrasonic continuous
Slurry (electrode slurry being uniformly mixed such as is poured into slurry pool by optional mode, while slurry pool is shaken using ultrasonic continuous),
By the continuous concussion of ultrasonic wave, deposition or the separation of electrode slurry can be prevented, it is ensured that spraying effect；
C., electrode slurry obtained is coated on to the obverse and reverse of papery substrate 3；
D. semi-finished product obtained by step c are dried and are cut to get.
In step c and d, preferably include successively it is following step by step：
C1. by one end rolled of papery substrate 3, it is placed in discharging device 4, the other end is furled in material collecting device 10, middle part
Be tensioned by transmitting device 9, and papery substrate 3 be transmitted to material collecting device 10 from discharging device 4, wherein from discharging device 4 to
The transmission road of material collecting device 10 is additionally provided with the first spray equipment 51, the first rolling device, the first drying unit 71, the successively through place
Two spray equipments 52, the second rolling device and the second drying unit 72, the first rolling device include the first initiative roll shaft 61 and the
One driven roll shaft 62, the second rolling device include the second initiative roll shaft 81 and the second driven roll shaft 82；
C2. by the first spray equipment 51, electrode slurry obtained is sprayed on to the front of papery substrate 3, then pass through
One rolling device is smooth by the electrode slurry roll-in of spraying, is dried finally by the first drying unit 71；
C3. by the second spray equipment 52, electrode slurry obtained is sprayed on to the reverse side of papery substrate 3, then pass through
Two rolling devices are smooth by the electrode slurry roll-in of spraying, dried finally by the second drying unit 72；
C4. by semi-finished product obtained by step c3 according to required size cut to get.
Specifically, preferably, the drying of the first drying unit 71 and the second drying unit 72 (being such as chosen as heater)
Temperature is 100~160 DEG C；First spray equipment 51 and the second spray equipment 52 are preferably reciprocally equal back and forth by drive nozzle
The even surface for being sprayed at papery substrate 3；First initiative roll shaft 61, the first driven roll shaft 62, the second initiative roll shaft 81 and second from
Action roller shaft 82 is preferably the roll shaft of flat surface, wherein the first initiative roll shaft 61 and the first driven roll shaft 62 match, by first
The electric slurry roll-in that spray equipment 51 sprays is smooth, and the second initiative roll shaft 81 and the second driven roll shaft 82 are matched the second spray
The electric slurry roll-in that coating device 52 sprays is smooth.
This method is by rotary shaft coating processes, and in conjunction with the setting of drying unit, simple production process is at low cost, production
Efficient, good product consistency, qualification rate height is, it can be achieved that large-scale production.
The principle of ultracapacitor made from above-mentioned paper substrate electrode is：By electrostatic charge electrode surface and electrolyte it
Between interface on moved to store and discharge electric energy, since the movement or migration of this electrostatic charge are reversible completely, because
This, it makes service life of the ultracapacitor with overlength and charging/discharging function many times.This kind of electric double layer super capacitor
Device generally forms (positive electrode and negative electrode) by two electrodes, be inserted between electrodes it is a kind of with ion infiltration and prevent short circuit
Barrier material, such as papery substrate 3 described above, optional such as paper, two electrode isolations are come, separating tissue and two electrodes
Between gap then filled by electrolyte, two electrodes are connected with external positive and negative anodes connecting plate, thus constitute paper substrate
The symmetrical ultracapacitor of plane.When charging to this kind of ultracapacitor, band will be generated on the interface of electrode and electrolyte
There are two layers of counterions, i.e., all cations to migrate to cathode, all anions are then migrated to anode, this is with regard to shape
At so-called " electric double layer ", due to the formation of this two electric layer, the opposite charges in positive and negative charge and electrolyte on electrode
Ion mutually attracts and electric double layer is made to stablize, and metastable potential difference is generated in positive and negative interpolar, to make the super electricity after charging
Container has voltage value.When electric discharge, charge migration on electrode and electric current is generated in external circuit, electrode on electrolyte interface
Ion transfer to electrolyte in be in electroneutral, at this moment the ion in the charge and electrolyte of electrode surface be at chaotic shape
State, to make the voltage of the ultracapacitor after electric discharge become zero.
It should be understood that for those of ordinary skills, it can be modified or changed according to the above description,
And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Illustrative description is carried out to patent of the present invention above, it is clear that the realization of patent of the present invention is not by aforesaid way
Limitation, as long as use patent of the present invention methodology and technical solution carry out various improvement, or it is not improved will this
The design of patent of invention and technical solution directly apply to other occasions, are within the scope of the invention.
Claims (8)
1. a kind of preparation method of paper substrate electrode for ultracapacitor, which is characterized in that include the following steps：
A. select the paper wood of hydrophilic and oleophobic as papery substrate；
B. the raw material including active electrode material, binder and solvent is uniformly mixed, electrode slurry is made；
C., electrode slurry described in step b is coated on to the obverse and reverse of the papery substrate described in step a；
D. semi-finished product obtained by step c are dried and are cut to get.
2. preparation method according to claim 1, which is characterized in that raw material described in step b further includes metal nano material.
3. preparation method according to claim 1, which is characterized in that step b is by homogenizer or dispersion machine by the original
Material is uniformly mixed, and shakes the electrode slurry obtained by ultrasonic continuous.
4. preparation method according to claim 1, which is characterized in that include that following distribution is rapid successively in step c：
C1. the papery substrate described in step a is tensioned by transmitting device, and it is transmitted to material collecting device from discharging device,
Wherein, the transmission road from the discharging device to the material collecting device is additionally provided with the first spray equipment, the first roll-in successively from
Device, the first drying unit, the second spray equipment and the second rolling device；
C2. by the first spray equipment described in step c1, electrode slurry described in step b is sprayed on to the papery base described in step a
The front of plate, then it is by the first rolling device described in step c1 that the electrode slurry roll-in of spraying is smooth, finally by step
First drying unit drying described in rapid c1；
C3. by the second spray equipment described in step c1, electrode slurry described in step b is sprayed on to the papery base described in step a
The reverse side of plate, then it is by the second rolling device described in step c1 that the electrode slurry roll-in of spraying is smooth.
5. preparation method according to claim 4, which is characterized in that the transmission road described in step c1 is additionally provided with second through place
Drying unit, step d are dried semi-finished product obtained by step c as second drying unit.
6. preparation method according to claim 5, which is characterized in that the drying temperature of step c2 and step d is 100~
160℃。
7. preparation method according to claim 1, which is characterized in that the active electrode material described in step b includes porous
At least one of activated carbon, carbon nanotube, graphite and graphene.
8. a kind of paper substrate electrode for ultracapacitor, including papery substrate, which is characterized in that the papery substrate is parent
Water hates the papery substrate of oil, the obverse and reverse of the papery substrate to be attached with electrode coating, and the electrode coating is by above-mentioned power
Electrode slurry described in step b is formed during profit requires 1.
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| CN114284075A (en) * | 2021-12-16 | 2022-04-05 | 深圳江浩电子有限公司 | Electrode slurry for paper-based supercapacitor, paper-based electrode, preparation method and application |
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